Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles
Pseudo-first-order rate constants (k(obs)) for piperidinolysis of PS- follow the relationship k(obs) - k(0)= k(n)(obs) Pip(T) (Pip(T) = total concentration of Pip) at a constant CTABr(T) (total concentration of cetyltrimethylammonium bromide), MX (inert salt concentration) and 35 degreesC. The value...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Published: |
Journal of Physical Organic Chemistry
2001
|
| Subjects: |
| _version_ | 1825719143114997760 |
|---|---|
| author | Khan, M.N. Yusoff, R. |
| author_facet | Khan, M.N. Yusoff, R. |
| author_sort | Khan, M.N. |
| collection | UM |
| description | Pseudo-first-order rate constants (k(obs)) for piperidinolysis of PS- follow the relationship k(obs) - k(0)= k(n)(obs) Pip(T) (Pip(T) = total concentration of Pip) at a constant CTABr(T) (total concentration of cetyltrimethylammonium bromide), MX (inert salt concentration) and 35 degreesC. The values of k(n)(obs) at different CTABrT (ranging from 0.005 to 0.02 M) and MX follow the relationship k(n)(obs) = (k(w)(n) + k(w)(n) Psi MX + KnsM K-N K-S(0)CTABr(T))/( 1 + Psi MX + K-S(0) CTABr(T)), where k(w)(n) = k(n)(obs) at CTABr(T) = MX = 0, Psi is an empirical parameter and K-S(0) is the CTABr micellar binding constant of PS- in the absence of MX. The magnitude of Psi is attributed to the ability of X- to expel PS- from micellar pseudophase to the aqueous pseudophase. The values of Psi vary in the order Psi (sodium cinnamate) >Psi (sodium 4-methoxybenzoate) >Psi (sodium 2-chlorobenzoate) >Psi (disodium isophthalate) >Psi (disodium phthalate) >Psi (sodium sulfate) >Psi (disodium fumarate). The values of k(M)(ns) K-N (k(M)(ns) = k(M)(n)/V-M, where k(M)(n) is the second-order rate constant for the reaction of Pip with PS- in the micellar pseudophase and V-M is the micellar molar volume in M-1 and K-N represents CTABr micellar binding constant of Pip) are not significantly affected by the presence of MX into the reaction mixtures. |
| first_indexed | 2024-03-06T05:15:09Z |
| format | Article |
| id | um.eprints-5757 |
| institution | Universiti Malaya |
| last_indexed | 2024-03-06T05:15:09Z |
| publishDate | 2001 |
| publisher | Journal of Physical Organic Chemistry |
| record_format | dspace |
| spelling | um.eprints-57572013-04-17T02:37:04Z http://eprints.um.edu.my/5757/ Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles Khan, M.N. Yusoff, R. TA Engineering (General). Civil engineering (General) Pseudo-first-order rate constants (k(obs)) for piperidinolysis of PS- follow the relationship k(obs) - k(0)= k(n)(obs) Pip(T) (Pip(T) = total concentration of Pip) at a constant CTABr(T) (total concentration of cetyltrimethylammonium bromide), MX (inert salt concentration) and 35 degreesC. The values of k(n)(obs) at different CTABrT (ranging from 0.005 to 0.02 M) and MX follow the relationship k(n)(obs) = (k(w)(n) + k(w)(n) Psi MX + KnsM K-N K-S(0)CTABr(T))/( 1 + Psi MX + K-S(0) CTABr(T)), where k(w)(n) = k(n)(obs) at CTABr(T) = MX = 0, Psi is an empirical parameter and K-S(0) is the CTABr micellar binding constant of PS- in the absence of MX. The magnitude of Psi is attributed to the ability of X- to expel PS- from micellar pseudophase to the aqueous pseudophase. The values of Psi vary in the order Psi (sodium cinnamate) >Psi (sodium 4-methoxybenzoate) >Psi (sodium 2-chlorobenzoate) >Psi (disodium isophthalate) >Psi (disodium phthalate) >Psi (sodium sulfate) >Psi (disodium fumarate). The values of k(M)(ns) K-N (k(M)(ns) = k(M)(n)/V-M, where k(M)(n) is the second-order rate constant for the reaction of Pip with PS- in the micellar pseudophase and V-M is the micellar molar volume in M-1 and K-N represents CTABr micellar binding constant of Pip) are not significantly affected by the presence of MX into the reaction mixtures. Journal of Physical Organic Chemistry 2001 Article PeerReviewed Khan, M.N. and Yusoff, R. (2001) Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles. Journal of Physical Organic Chemistry, 14 (2). pp. 74-80. ISSN 0894-3230, DOI https://doi.org/10.1002/1099-1395(200102)14:2<74::Aid-Poc333>3.0.Co;2-5 <https://doi.org/10.1002/1099-1395(200102)14:2<74::Aid-Poc333>3.0.Co;2-5>. http://onlinelibrary.wiley.com/store/10.1002/1099-1395(200102)14:2<74::AID-POC333>3.0.CO;2-5/asset/333_ftp.pdf?v=1&t=hbg6e6bl&s=19f857b9e08f0110963c4a9dfb19ff00f304c774 10.1002/1099-1395(200102)14:2<74::Aid-Poc333>3.0.Co;2-5 |
| spellingShingle | TA Engineering (General). Civil engineering (General) Khan, M.N. Yusoff, R. Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title | Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title_full | Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title_fullStr | Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title_full_unstemmed | Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title_short | Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS-) with piperidine in the presence of cationic micelles |
| title_sort | effects of inert organic and inorganic anions on the rates of intramolecular general base catalyzed reactions of ionized phenyl salicylate ps with piperidine in the presence of cationic micelles |
| topic | TA Engineering (General). Civil engineering (General) |
| work_keys_str_mv | AT khanmn effectsofinertorganicandinorganicanionsontheratesofintramoleculargeneralbasecatalyzedreactionsofionizedphenylsalicylatepswithpiperidineinthepresenceofcationicmicelles AT yusoffr effectsofinertorganicandinorganicanionsontheratesofintramoleculargeneralbasecatalyzedreactionsofionizedphenylsalicylatepswithpiperidineinthepresenceofcationicmicelles |